JP5913531B2 - Cellulosic resin composition - Google Patents

Description

  The present invention relates to a cellulosic resin composition containing a cellulosic resin and a non-cellulosic thermoplastic resin, and a method for producing the same.

  As resource and environmental problems such as fossil resource depletion and global warming become more serious, development of biomass-derived bioplastics that do not depend on petroleum resources has attracted attention in recent years. Therefore, the movement to use plant-derived polylactic acid, natural material-based cellulose, starch, and the like as plastic has been activated. However, many of these plastics currently have low moldability, productivity and heat resistance. In particular, cellulose resins such as cellulose esters are poor in moldability (thermoformability) as they are, and are usually thermoformed in a plasticized state by using a plasticizer in combination.

  For example, JP-A-2005-194302 (Patent Document 1) discloses a resin composition comprising a cellulose ester having an average substitution degree of 2.7 or less, a plasticizer (such as a phosphate ester), and a filler. Yes. Japanese Patent Application Laid-Open No. 2007-61943 (Patent Document 2) includes a cellulose ester having an average substitution degree of 2.7 or less, a non-cellulosic thermoplastic resin (such as polycarbonate), and a plasticizer (such as phosphate ester). An improved resin composition is disclosed.

  In these documents, cellulose esters having an average substitution degree of 2.7 or more are not assumed. A typical example of such a cellulose ester having an average degree of substitution of 2.7 or higher is cellulose triacetate (or triacetyl cellulose, TAC). Many such TACs are discarded from, for example, liquid crystal factories and the like, and development of recycling technology is required (for example, Hiroshima Prefectural Research Institute of Technology Eastern Industrial Technology Center research report No.22 p.24-28 (Non-Patent Document 1)). However, TAC is difficult to thermoform, and there is no effective technology that can combine TAC and other resins.

  On the other hand, a compound having a fluorene skeleton (such as a 9,9-bisphenylfluorene skeleton) is a material known to have an excellent function in refractive index, heat resistance, and the like. Examples of a method for expressing such an excellent function of the fluorene skeleton in a resin and making it moldable include, for example, bisphenol fluorene (BPF), biscresol fluorene (BCF), bisaminophenyl fluorene (BAFL), bisphenoxyethanol fluorene ( A method is known in which a fluorene compound having a reactive group (such as BPEF) having a reactive group (hydroxyl group, amino group, etc.) is used as a constituent component of a resin and a fluorene skeleton is introduced into a part of the skeleton structure of the resin. However, in such a method, even if a high function can be expressed, since the resin skeleton is replaced with a fluorene skeleton, the type of resin is limited.

In addition, in order to easily express the excellent function of the fluorene skeleton, an attempt has been made to add a compound having a fluorene skeleton to a general-purpose resin. For example, JP-A-2005-162785 (Patent Document 3) discloses a compound having a fluorene skeleton (for example, 9,9-bis (mono to trihydroxyphenyl) fluorenes or a C _2-4 alkylene oxide adduct thereof, 9,9-bis (mono to trihydroxyphenyl) fluorenes or glycidyl ethers of C _2-4 alkylene oxide adducts thereof, and thermoplastic resins (for example, polyester resins, polyurethane resins, polycarbonate resins, acrylic resins) Resin resin, polyimide resin, etc.) are disclosed.

  Note that this document does not disclose any cellulose resin as a thermoplastic resin to which a fluorene skeleton is added. In this document, a compound having a fluorene skeleton is simply used as a component for imparting a property derived from a compound having a fluorene skeleton (for example, a high refractive index) to the thermoplastic resin. Is not supposed to be plasticized.

JP-A-2005-194302 JP 2007-61943 A Japanese Patent Laying-Open No. 2005-162785 (claims, paragraph number [0007])

Hiroshima Prefectural Research Institute of Technology Eastern Industrial Technology Center Research Report No.22 p.24-28

  Accordingly, an object of the present invention is to provide a resin composition capable of efficiently combining a cellulosic resin and a non-cellulosic thermoplastic resin and a method for producing the same.

  Another object of the present invention is to provide a resin composition that can improve moldability or processability even when it contains a cellulose resin, and a method for producing the same.

  Still another object of the present invention is to provide a resin composition capable of combining a cellulosic resin and a non-cellulosic thermoplastic resin by melt-kneading (or melt mixing) and a method for producing the same.

  As a result of intensive studies to achieve the above-mentioned problems, the present inventors have unexpectedly found that the specific fluorene compound is surprisingly cellulose-based resin (particularly cellulose-based resin that has been difficult to efficiently plasticize in the past, such as cellulose acetate. Resin), and by combining such a fluorene compound, a cellulose resin, and a non-cellulosic thermoplastic resin, plasticization of the cellulose resin occurs and non-cellulosic thermoplasticity. The present invention was completed by finding that a resin composition in which a cellulose resin and a non-cellulosic thermoplastic resin are combined is obtained because the resin is plasticized or compatible with a fluorene resin.

  That is, the resin composition of the present invention (cellulose-based resin composition) includes a cellulose-based resin, a non-cellulosic thermoplastic resin (sometimes simply referred to as a non-cellulosic resin), and 9,9-bisaryl. And a fluorene compound having a fluorene skeleton. The cellulose resin may be composed of, for example, a cellulose ester (particularly, cellulose triacetate).

  The non-cellulosic thermoplastic resin may be composed of a thermoplastic resin having an aromatic ring (for example, an aromatic polycarbonate resin).

  Further, the fluorene compound may be at least one selected from, for example, 9,9-bis (hydroxyaryl) fluorenes and 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes.

  In the resin composition of the present invention, the ratio of the cellulose resin and the non-cellulosic thermoplastic resin is, for example, the former / the latter (weight ratio) = 99/1 to 40/60 (for example, 97/3 to 50). The ratio of the fluorene compound may be, for example, about 0.5 to 30 parts by weight (for example, 1 to 25 parts by weight) with respect to 100 parts by weight of the cellulose resin. Good.

  The present invention also includes a method for producing the resin composition by melt-mixing a cellulose resin, a non-cellulosic thermoplastic resin, and a fluorene compound having a 9,9-bisarylfluorene skeleton.

  In the present invention, by using a compound having a specific fluorene skeleton, a cellulose resin and a non-cellulose thermoplastic resin can be efficiently combined. Therefore, in this invention, the composite material by which the characteristic derived from a non-cellulosic thermoplastic resin was efficiently provided to the cellulose resin, and the composite material by which the characteristic of the cellulose resin was improved or improved can be obtained efficiently.

  In particular, in the resin composition of the present invention, a cellulose resin (particularly a cellulose resin in which the difference between the thermal decomposition temperature and the melting point or the softening point is close and the solvent solubility is inferior due to a decrease in crystallinity and the like. Even if it contains a resin, for example, a cellulose ester such as cellulose diacetate or cellulose triacetate, the moldability or processability can be improved. Moreover, in the present invention, not only the combination of the cellulose resin and the non-cellulosic thermoplastic resin, but also the combination of the fluorene compound, the properties such as transparency, heat resistance, water resistance, and surface hardness are achieved. An excellent cellulosic resin composition is obtained.

  In the present invention, although a cellulose resin having poor melt moldability is usually contained, the cellulose resin and the non-cellulosic thermoplastic resin can be combined by melt kneading. Therefore, in the present invention, a composite material of cellulosic resin can be obtained with extremely high practicality.

  The resin composition (cellulose-based resin composition) of the present invention includes a cellulose-based resin, a non-cellulosic thermoplastic resin, and a fluorene compound having a 9,9-bisarylfluorene skeleton. In the resin composition of the present invention, the fluorene compound seems to act as a component (plasticizer) for plasticizing at least the cellulose resin, as will be described later.

[Cellulosic resin]
The cellulose-based resin is not particularly limited, and various cellulose derivatives such as cellulose ester, cellulose carbamate (for example, cellulose phenyl carbamate), cellulose ether and the like can be used.

Examples of the cellulose ester include cellulose acetate such as cellulose diacetate (DAC) and cellulose triacetate (TAC); cellulose C _3-5 acylate such as cellulose propionate and cellulose butyrate; cellulose acetate propionate (CAP), Examples include cellulose acylate such as cellulose acetate C _3-5 acylate such as cellulose acetate butyrate (CAB).

Examples of the cellulose ether include alkyl cellulose (eg, C _1-4 alkyl cellulose such as methyl cellulose and ethyl cellulose), and hydroxyalkyl cellulose (eg, hydroxy C ₂₋ such as hydroxyethyl cellulose (HEC) and hydroxypropyl cellulose (HPC)). ₄ alkyl cellulose, etc.), hydroxyalkyl alkyl cellulose (eg, hydroxy C _2-4 alkyl C _1-4 alkyl cellulose, such as hydroxypropylmethyl cellulose), carboxyalkyl cellulose (such as carboxymethyl cellulose (CMC)), alkyl-carboxyalkyl cellulose (Such as methyl carboxymethyl cellulose), derivatives thereof [for example, sodium carboxymethyl cellulose, etc. CMC salt (alkali metal salt etc.), etc.].

Cellulosic resins can be used alone or in combination of two or more. Among the cellulose-based resins, cellulose esters and cellulose ethers are preferable, and cellulose esters (cellulose acylates) such as cellulose acetate and cellulose acetate C _3-4 acylate are particularly preferable. More specifically, cellulose esters such as cellulose diacetate, cellulose triacetate, cellulose acetate propionate, and cellulose acetate butyrate may be suitably used as the cellulose resin.

  Such a cellulose-based resin (cellulose ester or the like) has a thermal decomposition temperature close to a melting point or a softening point, and is difficult to be fluidized by heating. For this reason, compounding, molding, or processing methods that utilize the molten state or fluidity of a resin that is usually used for thermoplastic resins are often not applicable to cellulosic resins. Among them, cellulose acetate (particularly cellulose diacetate and cellulose triacetate) has low solubility in a solvent and is extremely difficult to fluidize by heating. Moreover, when plasticizing a cellulose derivative such as a cellulose ester with a conventional plasticizer, it is necessary to use a large amount of the plasticizer, and the resulting resin composition cannot maintain the characteristics of the cellulose resin. However, when a fluorene compound and a cellulose resin are combined, the crystallinity can be reduced by using the fluorene compound while maintaining the characteristics of the cellulose resin, and the glass transition temperature, the melting point, or the softening point is lowered. Since it can be melted (melted) or softened by heating, the fluidity can be greatly improved. Therefore, the cellulose resin can be plasticized even in the melt-kneading system despite the use of a cellulose resin such as cellulose ester (cellulose acetate or the like). Therefore, a cellulose resin and a cellulose resin composition containing a fluorene compound can be compounded, molded or processed in a melt-kneading system, and can be easily combined with a non-cellulosic thermoplastic resin. it can.

  In addition, since the crystallinity of the cellulose-based resin can be reduced (that is, the proportion of the amorphous portion is increased), the glass transition temperature and / or the melting point can be lowered. In particular, when cellulose diacetate is used, it can be non-crystallized as the melting point becomes difficult to observe. Further, even when cellulose triacetate, which has been extremely difficult to plasticize conventionally, can be lowered by the action of the fluorene compound, the glass transition temperature and the melting point can be lowered, and a high plasticizing effect can be obtained. Therefore, the resin composition of the present invention can be obtained by melt kneading as described later.

  In particular, the fluorene compound is effective for plasticizing a cellulosic resin (particularly cellulose acetate such as cellulose diacetate and / or cellulose triacetate). Further, external plasticization of cellulose triacetate, which has not been known at all, particularly plasticization in a melt-kneading system, has been achieved for the first time with a fluorene compound.

  Therefore, the cellulose resin may be composed of cellulose triacetate, in particular. The cellulose resin may be composed of only cellulose triacetate, or may be composed of cellulose triacetate and another cellulose resin (cellulosic resin other than cellulose triacetate). When combined with other cellulosic resins, the ratio of cellulose triacetate is, for example, 30% by weight or more (eg, 40 to 99.9% by weight), preferably 50% by weight or more (eg, 60 to 99.5% by weight), more preferably 70% by weight or more (for example, 80 to 99% by weight).

[Non-cellulosic thermoplastic resin]
The non-cellulosic thermoplastic resin can be appropriately selected depending on the purpose of compounding with the cellulose resin. Examples of such non-cellulosic thermoplastic resins include olefin resins (polyethylene, polypropylene, polymethylpentene, amorphous polyolefin, etc.), halogen-containing vinyl resins (for example, chlorine-containing resins such as polyvinyl chloride, Fluororesins, etc.), acrylic resins (for example, (meth) acrylic monomers alone or copolymers such as polymethyl methacrylate), styrene resins (for example, polystyrene, acrylonitrile-styrene resins, etc.), polycarbonate resins (Aromatic polycarbonate resins such as bisphenol A polycarbonate), polyester resins (for example, polyethylene terephthalate, polybutylene terephthalate, polycyclohexanedimethylene terephthalate, polyethylene naphthalate, etc. Aromatic polyester resins such as ruxylene arylate resins, polyarylate resins, liquid crystal polyesters; aliphatic polyester resins such as polylactic acid and polycaprolactone), polyacetal resins, polyamide resins (for example, polyamide 6, polyamide 66) , Polyamide 46, polyamide 6T, polyamide MXD, etc.), polyphenylene ether resin (modified polyphenylene ether, etc.), polysulfone resin (eg, polysulfone, polyethersulfone, etc.), polyphenylene sulfide resin (polyphenylene sulfide, etc.), polyimide resin (Polyetherimide, Polyamideimide, Polyamino bismaleimide, Bismaleimide triazine resin, etc.), Polyether ketone resin (Polyether ketone, Polyether ketone) And ether ketone), thermoplastic elastomer (polyamide elastomer, polyester elastomer, polyurethane elastomer, polystyrene elastomer, polyolefin elastomer, polydiene elastomer, polyvinyl chloride-based elastomer, fluorine-based thermoplastic elastomer), and the like. These thermoplastic resins may be used alone or in combination of two or more.

  Among these, thermoplastic resins containing an aromatic ring (benzene ring), for example, aromatic polycarbonate resins (such as bisphenol A polycarbonate), aromatic polyester resins [polyalkylene arylate resins, polyarylate resins, etc.] Polysulfone-based resins, polyphenylene sulfide-based resins, and the like are preferable, and thermoplastic resins (such as aromatic polycarbonates and aromatic polyester-based resins) that contain an aromatic ring and have a polar group in the molecule are particularly preferable. Since these aromatic ring-containing resins have an aromatic ring, they are highly compatible with fluorene compounds, and if they have a polar group, they also have an affinity for plasticized cellulosic resins. Excellent.

[Fluorene compound]
In the resin composition of the present invention, a cellulosic resin and a non-cellulosic thermoplastic resin are combined with a fluorene compound. That is, as described above, such a fluorene compound functions as a plasticizer for the cellulosic resin and is also compatible with a non-cellulosic thermoplastic resin or as a plasticizer for a non-cellulosic thermoplastic resin. For this reason, the cellulose resin and the non-cellulosic thermoplastic resin are efficiently combined. The fluorene compound is compatible with the cellulosic resin at a molecular level or close to the molecular level because of chemical interaction with the cellulosic resin. Therefore, it is possible to make a composite in a melt-kneading system of a cellulose resin (especially cellulose triacetate, etc.) and a non-cellulosic thermoplastic resin, which has heretofore been difficult.

  In addition, even if the ratio of the fluorene compound is large, bleeding out can be prevented or suppressed, and the cellulose resin can be effectively plasticized even with a relatively small amount.

  Therefore, in the present invention, not only the excellent properties (transparency, mechanical properties, etc.) of the cellulosic resin and non-cellulosic thermoplastic resin can be maintained while being combined with the non-cellulosic thermoplastic resin, but also by the use of a fluorene compound. In the resin composition, various properties such as fluidity (melt fluidity), water resistance, and surface hardness can be imparted or improved (or improved).

  Such a fluorene compound may be a compound having a 9,9-bisarylfluorene skeleton, and a monomer having a 9,9-bisarylfluorene skeleton (for example, 9,9-bis (hydroxyaryl) fluorenes described later) , 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes) may be used as a polymerization component, but usually, for example, a fluorene compound represented by the following formula (1) may also be used. Good.

(In the formula, A represents an aromatic hydrocarbon ring having at least a benzene ring skeleton, X ¹ represents a heteroatom-containing functional group, R ¹ represents an alkylene group, and R ² represents a hydrocarbon group (an alkyl group, Aryl group, etc.), ether group (substituted hydroxyl group), thioether group (substituted thiol group), acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano group or N, N-disubstituted amino group, R ³ Is a hydrocarbon group (alkyl group, aryl group, etc.), hydroxyl group, ether group (substituted hydroxyl group), mercapto group, thioether group (substituted thiol group), acyl group, alkoxycarbonyl group, halogen atom, nitro group, cyano A group, an amino group or a substituted amino group, k represents an integer of 0 or 1 or more, m represents an integer of 1 to 3, and n and p are the same Or, it is different and represents an integer of 0 to 4.)
In the above formula (1), as the aromatic hydrocarbon ring represented by ring A, in addition to a benzene ring, a condensed polycyclic aromatic hydrocarbon ring having at least a benzene ring skeleton [for example, a condensed bicyclic hydrocarbon Ring (C _8-20 condensed bicyclic hydrocarbon ring such as indene ring, naphthalene ring, etc., preferably C _10-16 condensed bicyclic hydrocarbon ring etc.), condensed tricyclic hydrocarbon ring (anthracene ring, phenanthrene ring) Etc.) and the like. Note that the two rings A substituted at the 9-position of fluorene may be different or the same, but usually they are the same ring in many cases. Of the rings A, a benzene ring, a naphthalene ring (particularly a benzene ring) and the like are preferable.

  In addition, the substitution position of the ring A substituted to 9th position of fluorene is not specifically limited. For example, when ring A is a naphthalene ring, the group corresponding to ring A substituted at the 9-position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like.

In the formula (1), examples of the hetero atom-containing functional group represented by X ¹ include a functional group having at least one selected from oxygen, sulfur and nitrogen atoms as a hetero atom. The number of heteroatoms contained in such a functional group is not particularly limited, but may be usually 1 to 3, preferably 1 or 2. Examples of the functional group include an oxygen atom-containing functional group such as a hydroxyl group and an epoxy-containing group (epoxy group, glycidyl group, etc.); a sulfur atom-containing functional group such as a mercapto group; an amino group or an N-monosubstituted amino group [ for example, (such as N- mono- _{C 1-4} alkylamino group) N- monoalkylamino group such as methylamino, ethylamino group, N- mono-hydroxyalkyl amino group such as hydroxyethylamino group (N- monohydroxy _{C 1} Nitrogen-containing functional groups such as _-4 alkylamino group and the like]. Of X ¹ , a hydroxyl group, an epoxy-containing group (such as a glycidyl group), an amino group, or an N-monosubstituted amino group is preferable, and a hydroxyl group is particularly preferable.

In the formula (1), examples of the alkylene group represented by the group R ¹ include C _2-6 alkylene groups such as ethylene group, propylene group, trimethylene group, 1,2-butanediyl group, and tetramethylene group, Is a C _2-4 alkylene group, more preferably a C _2-3 alkylene group. Of these alkylene groups, an ethylene group is particularly preferable. When k is an integer of 2 or more, the alkylene groups in each oxyalkylene unit may be the same or different, but are usually the same in many cases. In the two rings A, the groups R ¹ may be the same or different and are often the same.

K indicating the oxyalkylene group repeating number of (OR ¹⁾ (average addition mole number) is 0 to 15 (e.g., 0-10) can be selected from the range of about, for example 0-6, preferably 0-4 (e.g. 0-3), more preferably 0-2, in particular 0 or 1. The oxyalkylene groups bonded to the two rings A may be the same or different, but are usually the same in many cases.

In the formula (1), m, which represents the number of the group — (OR ¹ ) _k —X ¹ substituted on the ring A, is preferably an integer of 1 to 3, more preferably 1 or 2, 1 may be sufficient. In addition, the substitution position in the ring A of the group-(OR ¹ ) _k -X ¹ is not particularly limited. For example, when the ring A is a benzene ring, the bonding position with the 9th position of the fluorene skeleton (the 1st position) On the other hand, any of 2nd, 3rd and / or 4th position may be sufficient. For example, when m is 2, the substitution positions may be 2-position, 3-position, 2-position, 4-position, 3-position, 5-position, etc., but are often 3-position and 4-position. When ring A is a naphthalene ring, it may be substituted at an appropriate substitution position (tertiary carbon atom) of a benzene ring not directly bonded to ring A. Substitution at an appropriate substitution position (tertiary carbon atom) is preferred.

In the formula (1), the hydrocarbon group represented by R ² and R ³ is an alkyl group (for example, C ₁ such as methyl group, ethyl group, propyl group, isopropyl group, butyl group, t-butyl group). _-6 alkyl group, preferably C _1-4 alkyl group, more preferably C _1-3 alkyl group, particularly methyl group or ethyl group), cycloalkyl group (cyclopentyl group, cyclohexyl group etc.) C _5-8 Cycloalkyl group, preferably C _5-6 cycloalkyl group, etc., aryl group [eg, phenyl group, alkylphenyl group (mono or dimethylphenyl group (tolyl group, 2-methylphenyl group, xylyl group, etc.), naphthyl group) _{C 6-10} aryl group, etc., preferably a phenyl group, an aralkyl group (benzyl group, _{C 6-10} aryl such as phenethyl -C _1-4 such as an alkyl group), and others.

Examples of the ether group represented by R ² and R ³ include an alkoxy group, a cycloalkoxy group, an aryloxy group, and an aralkyloxy group. Examples of the alkoxy group include C _1-6 alkoxy groups such as a methoxy group, an ethoxy group, a propoxy group, an n-butoxy group, and a t-butoxy group (preferably a C _1-4 alkoxy group, more preferably a C _1-3 alkoxy group). Etc.), and examples of the cycloalkoxy group include C _5-8 cycloalkyloxy groups such as a cyclohexyloxy group (C _5-6 cycloalkyloxy group, etc.). Furthermore, examples of the aryloxy group include C _6-10 aryloxy groups such as a phenoxy group, and examples of the aralkyloxy group include C _6-10 aryl-C _1-4 alkyloxy groups such as a benzyloxy group. Etc. can be exemplified.

Moreover, as a thioether group (substituted thiol group or substituted mercapto group) represented by R ² and R ³ , a thioether group (an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, etc.) corresponding to the ether group, etc. Can be illustrated.

Examples of the acyl group represented by R ² and R ³ include C _2-7 acyl groups such as an acetyl group (C _2-5 acyl group) and the like. Examples of the alkoxycarbonyl group include C ₂ such as a methoxycarbonyl group. _{A 1-4} alkoxy-carbonyl group etc. can be illustrated.

Examples of the halogen atom represented by R ² and R ³ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

As the N, N-disubstituted amino group represented by R ² , an N, N-dialkylamino group (a diC _1-6 alkylamino group such as an N, N-dimethylamino group, preferably a diC _1-4). Alkylamino group), N, N-diacylamino group and the like. The substituted amino group represented by R ³ includes N-monosubstituted amino groups [for example, N-monoalkylamino groups such as methylamino and ethylamino groups (N-monoC _1-6 alkylamino groups, preferably the N- such mono _{C 1-4} alkylamino group), N- mono-hydroxyalkyl amino group (N- monohydroxy _{C 1-6} alkylamino group such as a hydroxyethyl group, preferably N- monohydroxy _{C 1-4} An alkylamino group, etc.], N, N-disubstituted amino group [N, N-dialkylamino group (a diC _1-6 alkylamino group such as N, N-dimethylamino group, preferably diC _1-4). An alkylamino group, etc.)].

The groups R ² may be different or the same in the two rings A substituted at the 9-position of the fluorene skeleton. Moreover, when the ring A has a plurality of groups R ² , some or all of the types of R ² may be the same or all may be different. The groups R ³ may be different or the same in the two benzene rings of the fluorene skeleton. In addition, when the benzene ring has a plurality of groups R ³ , the types of R ³ may be partially or completely the same or all different.

N indicating the number (number of substitutions) of the group R ² and p indicating the number of the groups R ³ may each preferably be an integer of 0 to 3, more preferably 0 to 2. n and p may be the same or different. N may be different in the two rings A substituted at the 9-position of the fluorene skeleton, but they are often the same. p may also be different or the same for the two benzene rings of the fluorene skeleton.

  In the formula (1), for example, the following compounds (a) to (e) are preferable.

(A) Ring A is a benzene ring or a naphthalene ring, X ¹ is a hydroxyl group, an epoxy-containing group, an amino group, or an N-monosubstituted amino group, and R ¹ is a C _2-4 alkylene group, R ² is an alkyl group, alkenyl group, aryl group, alkoxy group, halogen atom or cyano group, and R ³ is an alkyl group, alkenyl group, aryl group, hydroxyl group, alkoxy group, mercapto group, alkylthio group, halogen An atom, a cyano group, an amino group, or an N-monosubstituted amino group, k is an integer of 0 to 3, m is 1 or 2, and n and p are the same or different, and an integer of 0 to 3 A compound which is
(B) Ring A is a benzene ring or a naphthalene ring, X ¹ is a hydroxyl group, R ¹ is a C _2-4 alkylene group, R ² is a C _1-6 alkyl group, a phenyl group, a halogen atom Or a cyano group, R ³ is a C _1-6 alkyl group, a hydroxyl group, a halogen atom, a cyano group, an amino group or an N-monoC _1-6 alkylamino group, and k is an integer of 0-2. , M is 1, and n and p are the same or different and are an integer of 0 to 2;
(C) Ring A is a benzene ring, X ¹ is a hydroxyl group, R ¹ is a C _2-3 alkylene group, R ² is a C _1-4 alkyl group or a phenyl group, and R ³ is A compound having a C _1-4 alkyl group, a hydroxyl group, k is 0 or 1, m is 1, and n and p are the same or different and are 0 or 1;
(D) Ring A is a benzene ring, X ¹ is a hydroxyl group, R ¹ is a C _2-3 alkylene group, k is 0 or 1, m is 1, n and p are 0 And (e) Ring A is a benzene ring, X ¹ is a hydroxyl group, R ¹ is an ethylene group, R ² is a C _1-3 alkyl group, and R ³ is C _{1- A} compound having ₃ alkyl groups, k being 0 or 1, m being 1, n and p being the same or different and being 0 or 1.

Representative fluorene compounds include, for example, (A) 9,9-bis (hydroxyaryl) fluorenes {for example, 9,9-bis (hydroxyphenyl) fluorene [for example, 9,9-bis (4-hydroxyphenyl) ) Fluorene, etc.], 9,9-bis (alkyl-hydroxyphenyl) fluorene [e.g., 9,9-bis (3-methyl-4-hydroxyphenyl) fluorene, 9,9-bis (3,5-dimethyl-4) 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene], 9,9-bis (aryl-hydroxyphenyl) fluorene [eg 9,9-bis (3 - phenyl-4-hydroxyphenyl) fluorene such as 9,9-bis _{(C 6-10} aryl - hydroxyphenyl (A1) 9,9-bis (hydroxyphenyl) such as 9,9-bis (di to trihydroxyphenyl) fluorene [for example, 9,9-bis (3,4-dihydroxyphenyl) fluorene]. ) Fluorenes (or a compound in which A is a benzene ring, k is 0, X ¹ is a hydroxy group, and m is 1 to 3 in the formula (1)); 9,9-bis (hydroxynaphthyl) fluorene [for example, 9 , 9-bis (6-hydroxy-2-naphthyl) fluorene etc.], etc. (A2) 9,9-bis (hydroxynaphthyl) fluorenes (or in the above formula (1), A is a naphthalene ring, k is 0, X ¹ is hydroxy group, compounds wherein m is 1-3), etc.}, (B) 9,9-bis (hydroxy (poly) alkoxyaryl) fluorenes {e.g., 9,9 Scan (hydroxyalkoxy phenyl) fluorene [e.g., 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (BPEF) 9,9-bis (such as hydroxy _{C 2-4} alkoxyphenyl) fluorene, 9 , 9-bis (alkyl - hydroxyalkoxy phenyl) fluorene [e.g., 9,9-bis [3-methyl-4- (2-hydroxyethoxy) phenyl] fluorene such as 9,9-bis (mono- or _{di-C 1- 4-} alkyl-hydroxy _C2-4 alkoxyphenyl) fluorene], 9,9-bis (aryl-hydroxyalkoxyphenyl) fluorene [e.g., 9,9-bis ( _C6-10 aryl- _hydroxyC2-4 alkoxyphenyl)] Fluorene], 9,9-bis [di to tri (hydroxyalkoxy) thio Eniru] fluorene [e.g., 9,9-bis [di or tri (hydroxy _{C 2-4} alkoxy) phenyl] fluorene, etc.] such as (B1) 9,9-bis (hydroxy (poly) alkoxyphenyl) fluorenes (or In the formula (1), A is a benzene ring, k is 1 or more (for example, 1 to 4), X ¹ is a hydroxy group, and m is 1 to 3); 9,9-bis (hydroxyalkoxynaphthyl) fluorene [For example, (B2) 9,9- such as 9,9-bis [hydroxy C _2-4 alkoxynaphthyl] fluorene such as 9,9-bis [6- (2-hydroxyethoxy) -2-naphthyl] fluorene]. Bis (hydroxy (poly) alkoxynaphthyl) fluorenes (or A in the formula (1), A is a naphthalene ring, k is 1 or more (for example, 1 to 4), X ¹ is a hydroxy group and m is 1 to 3), etc.}.

  These fluorene compounds may be used alone or in combination of two or more.

[Ratio of each component]
In the resin composition of the present invention, the ratio of the cellulosic resin to the non-cellulosic thermoplastic resin is, for example, the former / the latter (weight ratio) = 99.9 / 0.1 to 10/90 (for example, 99.5). Can be selected from the range of about 20/80), for example, 99/1 to 30/70 (for example, 99/1 to 40/60), preferably 98/2 to 45/55 (for example, 97/3 to 50). / 50), more preferably about 96/4 to 55/45 (for example, 95/5 to 60/40), and usually 99/1 to 50/50 (for example, 98/2 to 60/40). , Preferably 97/3 to 65/35, more preferably about 96/4 to 70/30). In particular, from the viewpoint of increasing the planting degree of the resin composition and using the cellulose resin effectively, the proportion of the cellulose resin may be relatively large. In the present invention, a composite material with a non-cellulosic thermoplastic resin can be obtained efficiently even if the ratio of the cellulose-based resin (particularly cellulose triacetate) is increased.

  In the resin composition of the present invention, the proportion of the fluorene compound can be selected from a range of about 0.1 to 60 parts by weight (for example, 0.2 to 50 parts by weight) with respect to 100 parts by weight of the cellulose resin, for example, 0.3 to 40 parts by weight, preferably 0.5 to 30 parts by weight, and more preferably about 1 to 25 parts by weight.

  Moreover, the ratio of a fluorene compound can be selected from the range of about 0.5-200 weight part with respect to 100 weight part of non-cellulosic thermoplastic resins, for example, 1-100 weight part, Preferably it is 5-80 weight part More preferably, it may be about 7 to 60 parts by weight.

  In addition, the ratio of a fluorene compound is selected from the range of about 0.1-50 weight part (for example, 0.2-40 weight part) with respect to 100 weight part of total amounts of a cellulose resin and a non-cellulosic thermoplastic resin. For example, 0.3 to 35 parts by weight, preferably 0.5 to 30 parts by weight, more preferably about 1 to 25 parts by weight, and usually 1 to 40 parts by weight (for example, 2 to 35 parts by weight). Part, more preferably 3 to 30 parts by weight, particularly 5 to 25 parts by weight).

[Other ingredients]
The resin composition of the present invention is a conventional additive, for example, a stabilizer (antioxidant, ultraviolet absorber, light-resistant stability, etc.) if necessary within a range that does not impair the effects of the present invention, depending on the application to be used. Agents, thermal stabilizers, etc.), flame retardants, flame retardant aids, other plasticizers, impact modifiers, fillers (or reinforcing agents), dispersants, antistatic agents, foaming agents, antibacterial agents, lubricants, etc. Is mentioned. These additives may be used alone or in combination of two or more.

In this invention, you may mix | blend a stabilizer suitably from the point which can suppress coloring of a molded object among these additives. In particular, such a stabilizer is effective when, for example, a cellulose resin that is easily colored, such as cellulose triacetate, is used. Stabilizers include phenolic compounds, amine compounds, phosphorus compounds, sulfur compounds (for example, thiodi-C _2-4 carboxylic acid di-C ₁₀ such as di-lauryl-3,3′-thiodipropionic acid ester. _-20 alkyl esters), epoxy compounds [for example, epoxidized oils and fats (epoxidized soybean oil and the like), epoxidized fatty acid alkyl esters (epoxidized methyl stearate and the like), epoxidized polybutadiene and the like) and the like.

As the phenolic compound, a phenolic (hindered phenolic) compound {1,1,3-tris (having a plurality of branched alkylphenyl groups (a phenyl group substituted with a branched alkyl group or a phenyl group having a branched alkyl group)) Tris (2-alkyl-4-hydroxy-5-branched C _3-8 alkylphenyl) butane such as 2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1,3,5-trimethyl-2, Tris (3,5-di-branched C _3-8 alkyl-4-hydroxybenzyl) benzene, such as 4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 1,3,5 1,3,5-trialkyl-2, such as trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, 6- tris (3,5-di - branched _{C 3-8} alkyl-4-hydroxybenzyl) benzene; tetrakis [methylene-3- (3,5-di -t- butyl-4-hydroxyphenyl) propionate] methane Tetrakis [alkylene-3- (3,5-di-branched C _3-8 alkyl-4-hydroxyphenyl) propionate] C _1-4 alkane, pentaerythrityl tetrakis [3- (3,5-di-t Pentaerythrityltetrakis [3- (3,5-di-branched C _3-8 alkyl-4-hydroxyphenyl) propionate] and the like}, such as —butyl-4-hydroxyphenyl) propionate]; hydrazine compounds {N, N ′ -Bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine and the like}; Nord compound [n-octadecyl-3- (4'-hydroxy-3 ', 5'-di -t- butylphenol) propionate], and others. Phenol compounds are available, for example, as trade names “Irganox 1010”, “Irganox 1076”, “Irganox 1330”, etc., manufactured by Ciba Japan Co., Ltd.

  Examples of the amine compound include tetracarboxylic acid tri- or tetrapiperidyl ester [for example, 1,2,3,4-butanetetracarboxylic acid tetrakis (2,2,6,6-tetramethyl-4-piperidyl) ester, etc. Tetracarboxylic acid tetrakis (tetramethylpiperidyl) ester; poly [[6-[(1,1,3,3-tetramethylbutyl) amino] -1,3,5-triazine-2,4-diyl] [( 2,2,6,6-tetramethyl-4-piperidinyl) imino]] and the like hindered amine compounds (HALS); naphthylamine compounds (phenyl-α-naphthylamine etc.); diphenylamine compounds (p-isopropoxydiphenylamine etc.) P-phenylenediamine compounds (N, N′-diphenyl-p-phenylene Amines, etc.) and the like.

Examples of the phosphorus compound include a phosphorus compound having a branched alkylphenyl group {tris (2,4-branched C _3-8 alkyl-butylphenyl) phosphite [tris (2,4-di-t-butylphenyl)]. Phosphites and the like], tetrakis (2,4-di-branched C _3-8 alkylphenyl) -4,4′-C _2-4 alkylene phosphite [tetrakis (2,4-di-t-butylphenyl) -4 , 4′-biphenylene phosphite], etc.]; triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite; tri-2 , 4-dimethylphenylphosphine, tri-2,4,6-trimethylphenylphosphine, tri o- tolylphosphine, tri -m- tolyl phosphine, tri -p- tolylphosphine, tri -o- anisylphosphine, and the like phosphine compound such as tri -p- anisylphosphine.

These stabilizers can be used alone or in combination of two or more. Among these stabilizers, a phenolic compound having a branched alkylphenyl group (hindered phenolic compound), a hindered amine compound, a phosphorus compound having a branched alkylphenyl group, and the like are preferable. A combination with a series compound (for example, a phosphorus series compound having a branched alkylphenyl group) [in particular, a plurality of branched C _3-8 alkyl (such as t-butyl) hindered phenolic compounds having a phenyl group and a plurality of branched C A combination with a phosphorus compound having a _3-8 alkyl (such as t-butyl) phenyl group] is also preferable. The ratio (weight ratio) between the hindered phenol compound and the phosphorus compound (eg, phosphorus compound having a branched alkylphenyl group) can be selected from the range of the former / the latter = 99/1 to 1/99. For example, it may be about 20/80 to 95/5, preferably 30/70 to 90/10, and more preferably about 40/60 to 85/15 (particularly 50/50 to 80/20). As a stabilizer that combines a hindered phenol compound and a phosphorus compound having a branched alkylphenyl group, for example, trade name “Irganox B215” manufactured by Ciba Japan Co., Ltd. is available.

  The proportion of the stabilizer is, for example, 0.001 to 10 parts by weight (for example, 0.01 to 8 parts by weight), preferably 0 with respect to 100 parts by weight of the total of the cellulose resin and the non-cellulosic thermoplastic resin. It may be about 1 to 7 parts by weight (for example, 0.5 to 6 parts by weight), more preferably about 1 to 5 parts by weight (particularly 2 to 4 parts by weight).

[Method for Producing Resin Composition]
The resin composition of the present invention is obtained by mixing a cellulose resin, a non-cellulosic thermoplastic resin, and a fluorene compound.

  For mixing, if necessary, a solvent (solvent) used to prepare a dope of the cellulose resin may be used, but usually the cellulose resin is efficiently plasticized without adding a solvent. However, it can be combined with a non-cellulosic thermoplastic resin. In particular, in the present invention, the cellulose resin and the non-cellulose thermoplastic resin can be melt-kneaded by the action of the fluorene compound. Therefore, in particular, the resin composition of the present invention may be obtained by melt-mixing (melt-kneading) a cellulose resin, a non-cellulosic thermoplastic resin, and a fluorene compound. For the melt mixing, a method similar to a conventional method for preparing a thermoplastic resin composition, for example, a melt kneading method using an extruder (such as a single screw or twin screw extruder) can be used. The form of the obtained resin composition is not particularly limited. For example, a cellulose resin, a non-cellulosic thermoplastic resin, and a fluorene compound are supplied to an extruder and melt-kneaded in the extruder. A resin composition may be obtained.

  The melt mixing (melt kneading) temperature can be appropriately selected according to the decomposition start temperature and the melt start temperature of the resin composition. Usually, a temperature lower than the decomposition start temperature and higher than the melt start temperature is selected and decomposed. In many cases, the temperature is 80 to 150 ° C., preferably 90 to 140 ° C., more preferably about 95 to 135 ° C. lower than the starting temperature.

  Specifically, the melt mixing temperature may be, for example, 180 to 280 ° C, preferably 220 to 270 ° C, and more preferably about 240 to 260 ° C. In particular, when the cellulose-based resin is composed of cellulose triacetate, the melt mixing temperature is 200 to 330 ° C, preferably 220 to 320 ° C, more preferably 240 to 310 ° C, particularly 250 to 300 ° C (for example, 260 to 290 ° C). ) Degree.

  The resin composition of the present invention can be melt-kneaded despite containing a cellulosic resin, so that a conventional molding method applied to a thermoplastic resin composition (for example, extrusion molding, compression molding, etc.) Can be molded.

  As described above, by adding a stabilizer, coloring of the resin composition (particularly a resin composition containing cellulose triacetate) due to melt kneading can be suppressed, but further, an inert gas (helium, nitrogen, argon, etc.) ), It is possible to more effectively suppress coloring of the resin composition.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

(Processability evaluation)
Comparative Examples 1-2 and Examples 1-3
The components shown in Table 1 were used in the proportions shown in Table 1, and melt kneaded at the temperatures shown in the table using a twin-screw extruder (KZW15 / 30 MG manufactured by Technobel) to obtain a cellulose resin composition.

  In the table, “TAC” is cellulose triacetate (manufactured by Daicel Chemical Industries, Ltd., LT55), “PC” is polycarbonate (manufactured by Teijin Chemicals Ltd., Panlite L-1225L), “BPEF” is 9, 9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd.) is shown.

  Table 1 shows the appearance of the obtained resin composition.

  As is clear from the results in Table 1, in Examples 1 to 3, by using BPEF, a TAC / PC composite resin composition free from coloring and foaming could be obtained efficiently. On the other hand, in Comparative Examples 1 and 2, coloring and foaming occurred because TAC was decomposed at the melting temperature. In Comparative Example 2, the TAC / PC composite resin composition could not be obtained efficiently.

(Evaluation of thermal characteristics)
Thermal characteristics [melting point (Tm), melting of resin compositions obtained in Comparative Example 1, Example 1, and Example 2 (Comparative Example 3, Example 4, and Example 5, respectively) and TAC (Comparative Example 2) Heat (ΔHm)] was measured using a DSC apparatus (manufactured by Rigaku Corporation, DSC8230). The results are shown in Table 2.

  As is apparent from the results in Table 2, as the amount of BPEF added increased, TAC-derived Tm and ΔHm decreased, indicating that TAC and BPEF were highly compatible and plasticized.

  Since the resin composition of the present invention contains a specific fluorene compound, it can be effectively plasticized even if it is a cellulose resin that has been difficult to melt and knead conventionally. It can be efficiently combined with a thermoplastic resin. Therefore, in addition to the field formed by solution casting or the like, it can be used in fields where a molded product obtained by extrusion molding or compression molding is required, for example, optical applications such as a liquid crystal display. Moreover, since the resin composition of the present invention contains a specific fluorene compound and exhibits excellent properties such as a high refractive index, it is also useful as a new optical material. Furthermore, in the present invention, since a cellulose resin is used, bioplastic can be effectively used.

Claims (5)

A plasticizer for melt-kneading and plasticizing a cellulose ester containing at least one selected from cellulose acetate, cellulose C _3-4 acylate and cellulose acetate C _3-4 acylate, comprising 9,9-bisarylfluorene A plasticizer comprising a fluorene compound having a skeleton. Cellulose ester, plasticizer of claim 1 Symbol mounting comprises at least one member selected from the group consisting of cellulose diacetate and cellulose triacetate. The fluorene compound is represented by the following formula (1)

(In the formula, ring A is a benzene ring or naphthalene ring, X ¹ is a hydroxyl group, R ¹ is a C _2-4 alkylene group, coefficient k is 0-2, coefficient m is 1 or 2, and R ² is Represents a methyl group or a phenyl group, and the coefficient n represents 0 or 1)
The plasticizer of Claim 1 or 2 containing the compound represented by these. Fluorene compounds are 9,9-bis (hydroxyphenyl) fluorene, 9,9-bis (methyl-hydroxyphenyl) fluorene, 9,9-bis (phenyl-hydroxyphenyl) fluorene, 9,9-bis (hydroxynaphthyl) Fluorene, 9,9-bis (hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (methyl-hydroxy (poly) C _2-4 alkoxyphenyl) fluorene, 9,9-bis (phenyl- hydroxy _{(poly) C 2-4} alkoxyphenyl) fluorene, and 9,9-bis to any one of (hydroxy _{(poly) C 2-4} alkoxy-naphthyl) according to claim 1 to 3 is at least one selected from fluorene The plasticizer described. The plasticizer according to any one of claims 1 to 4 , wherein the amount of the fluorene compound used relative to 100 parts by weight of the cellulose ester is 0.5 to 50 parts by weight.